Nickel catalysts for polymerization

ABSTRACT

A method for the polymerization of cycloolefins in a presence of a nickel (0) compound or a compound which can be converted in situ into a nickel (0) compound, as a catalyst. The catalyst of the present invention exhibits very high catalytic activity towards polymerization of cycloolefins.

The invention relates to the use of nickel catalysts for the polymerization of cycloolefins.

Polymers obtainable by polymerization of cycloolefins, in the presence or absence of acyclic olefins, have in recent times attracted interest because new optical applications are placing ever higher demands on the property profile of the thermoplastics to be used. Polycycloolefins are extraordinarily thermally stable and optically isotropic, and highly resistant to water and organic solvents.

Owing to their high optical transparency, low double refraction and high softening temperatures, cycloolefin homopolymers and copolymers are particularly suitable as raw materials for producing optical lenses and optical waveguides and also as information storage media, for example for compact discs.

Attempts have been made in the past to polymerize cycloolefins with the aid of Ziegler systems based on titanium compounds, vanadium compounds and metallocenes, cf. H. Cherdron et al., Angew. Makromol. Chem. 223 (1994), 121-133 and the literature cited therein. Since the structural and property diversity of the polycycloolefins obtained increases with the number of catalysts suitable for cycloolefin polymerization and the polycycloolefins known hitherto do not yet meet all expectations, there was a need for cycloolefin polymerization catalysts which are structurally different from the known cycloolefin polymerization catalysts.

EP-A-445 755 describes a process for the polymerization of cycloolefins of the norbomene type in the presence of a catalyst based on a transition metal of groups Vb, VIb, VIlb or VIII and an aluminoxane as cocatalyst. The preferred transition metals are nickel and palladium. The highest activity is shown by the catalyst system of Example 1 (23.6 kg of polymer/g of nickel, based on a polymerization time of 4 hours). For a polymerization on an industrial scale, an improved activity would be desirable. WO/14 048 discloses a process for the polymerization of cyclic olefins according to which use is made of a catalyst system based on an ionic transition metal (VIII) compound and a chain-transfer agent. Although polymerization using these catalyst systems appears promising, the catalyst activities are too low for use on an industrial scale. A further object of the invention was thus to provide suitable catalysts having improved activity for the polymerization of cycloolefins.

It has now been found that selected nickel compounds are highly active catalysts for the polymerization of cycloolefins: the weight ratio of catalyst used to polymer produced becomes extremely low.

The invention accordingly provides for the use of reaction products of

A. a nickel(0) compound or a compound which can be converted in situ into a nickel(0) compound, with, optionally,

B. a compound of the formula ##STR1## and (obligatorily) C. a compound of the formula ##STR2## as catalysts for the polymerization of cycloolefins, where R¹ to R⁶ are, independently of one another, straight-chain or branched C₁ -C₂₀ -alkyl, C₁ -C₂₀ -alkoxy, C₃ -C₈ -cycloalkyl, C₂ -C₂₀ -alkenyl, di-(C₁ -C₄ -alkyl)amino, C₆ -C₁₂ -aryloxy, C₇ -C₁₅ -aralkyl or C₇ -C₁₅ -aralkoxy,

E and F are, independently of one another, nitrogen, phosphorus, arsenic or antimony,

X is oxygen, sulphur, ═NR⁹, ═CR⁹ R¹⁰, ═C═C═O, ═C═C═S, ═C═PR¹ R² R³,

Y is oxygen or NR⁹,

R⁷, R⁸ are, independently of one another, hydrogen, C₁ -C₂₀ -alkyl, C₂ -C₂₀ -alkenyl, C₁ -C₂₀ -alkoxy, C₃ -C₈ -cycloalkyl, C₆ -C₁₂ -aryl, C₆ -C₁₂ -aryloxy, C₆ -C₁₂ -ar-C₁ -C₂₀ -alkyl, C₆ -C₁₂ -ar-C₁ -C₂₀ -alkoxy, C₁ -C₂₀ -alkyl-C₆ -C₁₂ -aryl, C₁ -C₂₀ -alkyl-C₆ -C₁₂ -aryloxy, chlorine, cyano, NHR², NR¹² ₂, OR¹², COOR¹², COOR¹¹, CONR¹², COR¹², SR¹², SO₂ R¹², OSO₂ R¹², P(O)(OR¹²)_(2-y) R¹³ _(y),

R⁷ may also be SO₃ R¹¹ or

R⁷ and R⁸ together with the two carbon atoms to which they are bound form an isocyclic or heterocyclic ring,

R⁹ and R¹⁰ are, independently of one another, R¹ or hydrogen, silyl, acyl, chlorophenyl, nitrophenyl, C₁ -C₆ -alkylphenyl, cyano, phenyl-C₂ -C₆ -alkenyl, silyl, trihalogenosilyl, tri-C₁ -C₃₀ -organosilyl, C₁ -C₁₆ -acyl, cyano, halogen, tri-C₁ -C₃₀ -organostannyl, -BH₂, di-C₁ -C₂₀ -organoboranyl, dihalogenoboranyl,

R¹¹ is an alkali metal, thallium, 1/2 alkaline earth metal, ammonium, phosphonium, C₁ -C₁₂ -alkyl or C₆ -C₁₂ -aryl,

R¹², R¹³ are, independently of one another, C₁ -C₂₀ -alkyl, C₂ -C₂₀ -alkenyl, C₃ -C₈ -cycloalkyl or C₆ -C₁₂ -aryl and

y is zero, 1 or 2.

The term alkyl in the definitions of R¹ to R³ represents straight-chain or branched alkyl having preferably from 1 to 12, particularly preferably from 1 to 6 and in particular from 1 to 4, carbon atoms. Examples which may be mentioned are methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, t-pentyl, hexyl, i-octyl, n-decyl and n-dodecyl.

The term alkenyl in the definitions of R¹ to R¹³ represents straight-chain or branched alkenyl having preferably from 2 to 18, particularly preferably from 2 to 12 and very particularly preferably from 2 to 6, carbon atoms. Examples which may be mentioned are vinyl, allyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, ethinyl, 1-propinyl, 2-propinyl, 1-butinyl, 2-butinyl, 3-butinyl, methallyl, crotyl and cinnamyl.

The term cycloalkyl in the radicals R¹ to R¹³ represents cycloalkyl having preferably from 3 to 7, in particular 3, 5 or 6, carbon atoms. Examples which may be mentioned are unsubstituted or substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

The term aryl in the radicals R¹ to R¹³ represents unsubstituted or substituted aryl having preferably from 6 to 10 carbon atoms in the aryl part. Preferred examples include phenyl and naphthyl. The aryl groups can bear from 1 to 3 substituents selected from the group consisting of halogen (in particular chlorine and/or fluorine), C₁ -C₄ -alkoxy, cyano, nitro or amino. The term aryl also includes heteroaryl, where heteroaryl represents heteroaryl which has from 1 to 5 carbon atoms and from 1 to 4 hetero atoms selected from the group consisting of oxygen, sulphur and nitrogen and may optionally be monosubstituted or polysubstituted by identical or different substituents and to which a 5- to 6-membered, saturated or unsaturated carbocycle is optionally fused, where heteroaryl preferably represents pyridyl, pyrimidyl, pyrazinyl, quinolyl, isoquinolyl, pyrrolyl, indolyl, pyrazolyl, imidazolyl, benzimidazolyl, triazolyl, thienyl, benzothienyl, furyl, benzofuryl, thiazolyl, benzothiazolyl, isothiazolyl, oxazolyl, benzoxazolyl, isoxazolyl, thiadiazolyl, isothiadiazolyl, oxadiazolyl or isoxadiazolyl, each of which may optionally be monosubstituted to trisubstituted by identical or different substituents, where heteroaryl substituents which may be mentioned are: fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, mercapto, amino, straight-chain or branched alkoxy or straight-chain or branched alkylthio each having from 1 to 4 carbon atoms, straight-chain or branched halogenoalkoxy or straightchain or branched halogenoalkylthio each having from 1 to 4 carbon atoms and 1 to 9 fluorine and/or chlorine atoms, phenyl, phenoxy, phenylthio, phenyl-C₁ -C₂ -alkoxy or phenyl-C₁ -C₂ -alkylthio.

The term aralkyl in the radicals R¹ to R¹³ represents compounds having preferably from 1 to 12, in particular from 1 to 6, carbon atoms in the straight-chain or branched alkyl part and preferably phenyl or naphthyl as aryl part. Examples of such aralkyl groups include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, 2-phenylethyl, α- and β-naphthylmethyl. These aralkyl radicals can bear from 1 to 3 substituents selected from the group consisting of halogen (in particular chlorine and/or fluorine), nitro, cyano, optionally halogenated C₁ -C₄ -alkyl or -alkoxy such as methyl, ethyl, trifluoromethyl, difluorochloromethyl, difluorochloromethyl, trichloromethyl, methoxy, ethoxy, trifluoromethoxy, difluorochloromethoxy or difluoromethoxy, optionally halogenated C₁ -C₄ -alkylmercapto such as methylmercapto, trifluoromethylmercapto, difluorochloromethylmercapto.

The term alkylaryl in the radicals R¹ to R¹³ represents the abovementioned aryl groups which in turn bear from 1 to 3 substituents selected from the group consisting of C₁ -C₄ -alkyl, halogeno-C₁ -C₂ -alkyl (such as trifluoromethyl, difluoromethyl).

The term alkoxy in the radicals R¹ to R¹³ represents straight-chain and branched alkoxy having preferably from 1 to 6, in particular from 1 to 4, carbon atoms. Preferred examples include methoxy, ethoxy, n- and i-propoxy, n-, i-, sec- and tert-butoxy as well as hexoxy.

The term aryloxy in the radicals R¹ to R¹³ represents compounds having preferably from 1 to 10 carbon atoms in the aryl part. Preferred examples are phenoxy and naphthoxy. The aryloxy groups can bear from 1 to 3 substituents selected from the group consisting of halogen (preferably chlorine and/or fluorine), C₁ -C₄ -alkyl, halogeno-C₁ -C₂ -alkyl (such as difluoromethyl and trifluoromethyl), cyano, nitro or amino.

The term alkylamino in the radicals R¹ to R¹³ represents monoalkylamino and dialkylamino radicals each preferably having from 1 to 4 carbon atoms in the respective straight-chain or branched alkyl parts, where in the case of dialkylamino, the two radicals together with the nitrogen atom to which they are bound may form a 5- or 6-membered, saturated ring which optionally contains an oxygen, sulphur or nitrogen atom and which is optionally substituted by one or two methyl groups, or represents straight-chain or branched alkenyloxy or straight-chain or branched alkinyloxy each having from 3 to 4 carbon atoms. The term alkylamino thus includes, for example, methylamino and dimethylamino, ethylamino and diethylamino, n-propylamino and di-n-propylamino, i-propylamino and di-i-propylamino, methylbutylamino, ethylbutylamino, pyrrolidino, piperidino, morpholino, thiomorpholino, N-methylpiperazino, 2,6-dimethylmorpholino.

The term arylamino in the radicals R¹ to R¹³ represents

    --NR.sup.14 R.sup.15

where

R¹⁴ represents hydrogen or C₁ -C₁₂ -alkyl, preferably hydrogen or methyl, and

R¹⁵ represents aryl or heteroaryl having preferably from 3 to 10 carbon atoms, in particular

(i) phenyl which is optionally monosubstituted to pentasubstituted by identical or different halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl groups each having 1 or 2 carbon atoms and from 1 to 5 identical or different halogen atoms, by halogen, cyano, nitro, amino, hydroxy, carbamoyl and/or thiocarbamoyl or by doubly linked dioxyalkylene which has 1 or 2 carbon atoms and may optionally be monosubstituted to tetrasubstituted by halogen and/or halogenomethyl, where the oxygen atoms are not adjacent, for example unsubstituted phenyl itself or phenyl which is monosubstituted to tetrasubstituted by identical or different difluoromethyl, trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochioromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulphinyl, trifluoromethylsulphonyl, fluorine, chlorine, bromine, cyano, nitro, carbamoyl and/or thiocarbamoyl substituents or by a doubly linked radical of the formula --O--CH₂ --O--, --O--CF₂ --O--, --O--CH₂ --CH₂ --O--, --O--CFC1--CFC1--O--, ##STR3## or --O--CF₂ --CF₂ --O--; or (ii) heteroaryl having from 2 to 10 carbon atoms and from 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, where these heteroaryl radicals may be monosubstituted to trisubstituted by identical or different halogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylsulphinyl or halogenoalkylsulphonyl groups each having 1 or 2 carbon atoms and from 1 to 5 identical or different halogen atoms, by halogen, cyano, nitro, amino, hydroxy, carbamoyl and/or thiocarbamoyl, for example pyrrolidinyl, piperidinyl, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5-oxadiazolyl, azepinyl, pyrrolyl, isopyrrolyl, pyridyl, piperazinyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-, 1,2,4- and 1,2,3-triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, oxepinyl, thiepinyl, 1,2,4-diazepinyl, quinolyl, isoquinolyl, quinazolyl, quinoxalyl, cinnolyl, tetrazolyl, indolyl, indazolyl, benzimidazolyl, benzothienyl, benzofuryl, benzothiazolyl, benzoxazolyl, thiadiazolyl, isothiadiazolyl, oxadiazolyl and isoxadiazolyl and their substitution products.

The preferred arylamino is anilino.

Component A

Nickel(0) compounds which may be mentioned by way of example are Ni(cyclooctadiene)₂ and Ni(allyl)₂. Examples of nickel compounds which can be converted in situ into nickel(0) compounds are: nickel acetylacetonate, nickel octanoate and nickel stearate which can be reduced by means of customary reducing agents such as boranate, alanate, aluminium alkyls or organolithium compounds.

Component B

Preferably, R¹ to R³ are, independently of one another, C₆ -C₁₂ -aryl or C₁ -C₆ -alkyl.

E is preferably phosphorus.

In a preferred embodiment, X represents CH₂, CH-phenyl, CH-trimethylsilyl and C(CN)₂, CH-vinyl, CH-propenyl and CH-styryl and CH-acyl, in particular CH-formyl, CH-acetyl, CH-benzoyl, CH-carbomethoxy, and also C(acetyl)₂ and C(benzoyl)₂, C(trimethylsilyl)₂, NH, N-methyl, N-ethyl, N-propyl, N-butyl, N-t-butyl, N-trimethylsilyl, N-triphenylsilyl, N-phenyl, N-tolyl or oxygen.

Component C

Preferably, R⁴ to R⁶ represent, independently of one another, C₆ -C₁₂ -aryl or C₁ -C₆ -alkyl; R⁴ is particularly preferably C₆ -C₁₂ -aryl.

Q is preferably phosphorus.

R⁷ and R⁸ preferably represent, independently of one another, hydrogen, C₁ -C₆ -alkyl, C₆ -C₁₂ -aryl,

R⁷ may also be C₁ C₁₃ -acyl or SO₃ Na, S₃ --C₁ -C₁₂ -alkyl, SO₃ -N+(C₁ -C₁₂ -alkyl)₄,

R⁸ may also be OR¹² and

R⁷ and R⁸ together with the two carbon atoms to which they are bound may also form a 5- or 6-membered ring.

As compounds of the formula (II) in which R⁷ and R⁸ together with the two carbon atoms form a ring, use can be made, for example, of the adducts of a quinoid compound or maleic anhydride with a phosphine of the formula R⁴ R⁵ R⁶ P.

Reaction Product of A, Optionally B and C

To prepare the catalyst, from 0 to 4 mol of the compound of the formula (I) and from 1 to 4 mol of the compound of the formula (II) are used per mol of nickel(0) compound, preferably about 1 mol of the compound of the formula (I) and about 1 mol of the compound of the formula (II) per mol of the nickel(0) compound.

The temperature in the preparation of the catalyst is from 0 to 100° C., preferably from 20 to 70° C. The preparation is carried out with exclusion of oxygen, preferably in a solvent which has to be inert toward the reactants, for example benzene, toluene, cyclohexane or n-hexane. After its preparation, the catalyst is usually isolated as a solid by filtration; if necessary, the solution may be concentrated and/or cooled beforehand. However, the catalyst can also be used directly without isolation, i.e. as solution or suspension, for the polymerization according to the invention.

The preferred nickel compounds where Q=phosphorus and Y=oxygen have, according to present knowledge, the structural feature of a chelating phosphorus-oxygen ligand of the formula ##STR4## According to a particularly preferred embodiment, use is made of catalysts which are prepared using not only component C (formula II) but also component B (formula I). Such particularly preferred catalysts correspond to the formula (IV) ##STR5## where E, Q, X, Y and R¹ to R⁸ are as defined above. Particularly preferred catalysts are compounds of the formula (IV) in which E and F are phosphorus,

X is oxygen, NR⁹, CR⁹ R¹⁰ and

Y is oxygen or NR⁹.

Most of the catalysts to be used according to the invention and the methods for their preparation are known from European Patent Specifications 101 927, 137 389 and 193 047 or they can be prepared, if not yet described in the literature, by methods similar to the known methods.

The reaction products of A, C and optionally B to be used according to the invention can be used as sole polymerization catalysts. However, it is frequently found that the concomitant use of cocatalysts gives a further improved result.

Suitable cocatalysts are in principle compounds having acid character (both Lewis and Bronstedt acids). Such acid compounds include, for example, organic aluminium halides such as RAlCl₂, R₂ AlCl, R₃ Al₂ Cl₃ (in each case R=C₁ -C₂₀ -, preferably C₁ -C₄ -alkyl). Preferred cocatalysts also include the compounds described in U.S. Patent Specification 5,155,188 and having the formulae

    (R.sub.n MO).sub.a R.sup.1.sub.b AlX.sub.c or (RO).sub.a R.sup.1 AIX.sub.c

where

m is silicon, tin, germanium, lead or aluminium,

R, R¹ are, independently of one another, alkyl, alkylene, alkinyl, aryl, aralkyl, aralkylene or aralkinyl each having up to 18 carbon atoms, preferably C₁ -C₃ -alkyl or phenyl and, if M=Al, either R or R¹ is halogen,

X is chlorine, fluorine, bromine or iodine, preferably chlorine,

a is from 0.5 to 2.5, preferably from 1 to 0.75,

b is from 0.25 to 2, preferably from 0.5 to 1,

c is from zero to 2, preferably from 0.72 to 1.25, a+b+c is 3,

n is 2 (if M=Al) or 3.

Replacement of the groups (RO) by R₃ SiO enables cocatalysts containing siloxy groups to be effectively prepared.

Further preferred cocatalysts are aluminoxanes, i.e. 1:1 reaction products of organoaluminium compounds with water, e.g. methylaluminoxane (MAO).

Furthermore, activation is generally effected by introducing (usually bulky) weakly coordinating or non-coordinating anions into the ligand field of the central metal so that, taking a heuristic view, one coordination site is easily made free or is available for the interaction with the monomer to be polymerized.

The generation of such anions in the vicinity of the central metal is achieved, for instance, by reaction with Bronstedt acids HX, where X can be, for example, trifluoromethylsulphonate. Other anions suitable as cocatalysts are, for instance, PF₆ ⁻, SbF₆ ⁻, SnCl₃ ⁻ and perchlorate.

Such anions can also be introduced using salts of the respective anion, e.g. alkali metal, alkaline earth metal, thallium, silver, phosphonium and ammonium salts.

Further preferred cocatalysts include boron compounds of the type BR₃ such as tris-(pentafluorophenyl)-borane or of the type HBR₄, where BR₄ is tetrafluoroborate, tetra-phenylborate, or tetrakis-[3,5-di-(trifluoromethyl)-phenyl]-borate.

Also preferred are the salts of such borates cat^(+BR) ₄ ⁻ - whose cations cat⁺ are, for instance, selected from the group consisting of Na, K, Li, Mg, Ca, Ag, Tl, triphenyl-methyl, N⁺ (C₁ -C₁₂ -alkyl)₄ and, in particular, N,N-dialkyl-anilinium ions.

Catalyst and cocatalyst can be added separately or together. During the reaction, catalyst and cocatalyst can be present in the form of a complex. It is possible to form this complex in situ or to form it in a separate reaction and to add it to the reaction in this pre-prepared form (in solution) or isolated (as solid).

Cycloolefins to be polymerized using the catalysts of the invention include all cycloolefins such as cyclobutene, cyclopentene and cyclopentadiene, but also polycyclic cycloolefins as are described in EP-A-608 903, i.e.

bicyclo-2-heptenes,

tricyclo-3-decenes,

tricyclo-3-undecenes,

tetracyclo-3-dodecenes,

pentacyclo-4-pentadecenes,

pentacyclopentadecadienes,

pentahydro-3-pentadecenes,

pentacyclo-4-hexadecenes,

pentacyclo-3-hexadecenes,

hexacyclo-4-heptadecenes,

heptacyclo-5-eicocenes,

heptacyclo-4-eicocenes,

heptacyclo-5-heneicocenes,

octacyclo-5-dococenes,

nonacyclo-5-pentacosenes,

nonacyclo-6-hexacosenes,

cyclopentadiene/acenaphthylene adducts,

1, 4-methano-1.4.4a.9a-tetrahydrofluorenes and

1, 4-methano-1.4.4a.5.10.10a-hexahydroanthracenes, for example

bicyclo[2.2.1]hept-2-ene,

6-methylbicyclo[2.2.1]hept-2-ene,

5,6-dimethylbicyclo[2.2.1]hept-2-ene,

1-methylbicyclo[2.2.1]hept-2-ene,

6-ethylbicyclo[2.2.1]hept-2-ene,

6-n-butylbicyclo[2.2.1]hept-2-ene,

6-isobutylbicyclo[2.2.1]hept-2-ene,

7-methylbicyclo [2.2.1]hept-2-ene,

tricyclo[4.3.0.1²,5 ]-3-decene,

2-methyltricyclo[4.3.0.1²,5 ]-3-decene,

5-methyltricyclo[4.3.0.1²,5 ]-3-decene,

tricyclo[4.3.0.1²,5 ]-3-undecene,

10-methyltricyclo[4.4.0.1²,5 ]-3-undecene,

tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-deodecene,

8-methyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-propyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-butyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isobutyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-hexyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-cyclohexyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-stearyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

5,10-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

2,10-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8,9-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-methyl-9-ethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

11,12-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

2,7,9-trimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

9-ethyl-2,7-dimethyltetracyclo[4.4.0.1².5.1⁷,10 ]-3-dodecene,

9-isobutyl-2,7-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

9,11,12-trimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

9-ethyl-11,12-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

9-isobutyl-11,12-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

5,8,9,10-t etramethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidenetetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidene-9-methyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidene-9-ethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidene-9-isopropyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidene-8-butyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidenetetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidene-9-methyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidene-9-ethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidene-9-isopropyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidene-9-butyltetracyclo[4.4.0.1².5.1⁷,10 ]-3-dodecene,

8-isopropylidenetetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isopropylidene-9-methyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isopropylidene-9-ethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isopropylidene-9-isopropyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isopropylidene-9-butyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-chlorotetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-bromotetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-fluorotetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8,9-dichlorotetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

pentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecene,

1,3-dimethylpentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecene,

1,6-dimethyl[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecene,

14,15-dimethyl[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecene,

pentacyclo[7.4.0.1²,5.1⁹,12.0⁸,13 ]-3-pentadecene,

methyl-substituted pentacyclo[7.4.0.1²,5.1⁹,12.0⁸,13 ]-3-pentadecene,

pentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4,10-pentadecadiene,

pentacyclo[8.4.0.1²,5.1⁹,12.0⁸,13 ]-3-hexadecene,

11-methylpentacyclo [8.4.0.1²,5.1⁹,12.0⁸,13 ]-3-hexadecene,

11-ethyl[8.4.0.1²,5.1⁹,12.0⁸,13 ]-3-hexadecene,

10,11-dimethyl[8.4.0.1²,5.1⁹,12.0⁸,13 ]-3-hexadecene,

pentacyclo[6.6.1.1³,6.0²,7.0⁹,14 ]-4-hexadecene,

1,3-dimethylpentacyclo[6.6.1.1³,6.0²,7.0⁹,14 ]-4-hexadecene,

15,16-dimethylpentacyclo[6.6.1.1³,6.0²,7.0⁹,14 ]-4-hexadecene,

hexacyclo[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene,

12-methylhexacyclo[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene,

12-ethylhexacyclo[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene,

12-isobutylhexacyclo[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene,

1,6,10-trimethylhexacyclo[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene,

heptacyclo[8.7.0.1²,9.1⁴,7.1¹¹,17.0³,8.0¹²,16 ]-5-eicosene,

heptacyclo[8.7.0.1³,6.1¹⁰,17.1¹²,15.0²,7.0¹¹,16 ]-4-eicosene and its dimethyl-substituted derivatives,

heptacyclo[8.8.0.1²,9.1⁴,7.1¹¹,18.0³,8.0¹²³,17 ]-5-heneicosene,

heptacyclo[8.8.0.1⁴,7.1¹¹,18.1¹³,16.0³,8.0¹²,17 ]-5-heneicosene and its trimethyl-substituted derivatives,

15-methylheptacyclo[8.8.0.1⁴,7.1¹¹,18.1¹³,16.0³,8.0.sup.12,17 ]-5-heneicosene

5-phenyl-bicyclo[2.2.1]hept-2-ene,

5-methyl-5-phenyl-bicyclo[2.2.1]hept-2-ene,

5-benzyl-bicyclo[2.2.1]hept-2-ene,

5-tolyl-bicyclo[2.2.1]hept-2-ene,

2-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene,

5-(isopropylphenyl)-bicyclo[2.2.1]hept-2-ene,

5-biphenyl-bicyclo[2.2.1]hept-2-ene,

5-(β-naphthyl)-bicyclo[2.2.1]hept-2-ene,

5-(α-naphthyl)-bicyclo[2.2.1]hept-2-ene,

5-(anthracenyl)-bicyclo[2.2.1]hept-2-ene,

5,6-diphenyl-bicyclo[2.2.1]hept-2-ene,

1,4-methano-1.4.4a.9a-tetrahydrofluorene,

1,4-methano-1.4.4a.5.10.10a-hexahydroanthracene,

8-phenyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-methyl-8-phenyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-benzyl-tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-tolyl-tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-(ethylphenyl)-tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-(isopropylphenyl)-tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8,9-diphenyl-tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-(biphenyl)-tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-(β-naphthyl)-tetracyclo[4.4.0.1²,5.1⁷,10]- 3-dodecene,

8-(α-naphthyl)-tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene and

8-(anthracenyl)-tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene.

Preferred cycloolefins also include those which are substituted by halogen, --CF₃, --N(C₁ --C₃₀ -alkyl)₂,--CN, C₁ -C₁₂ -alkoxy or C₁ --C₂₀ -alkylene-COOC₁ -C₂₀ -alkyl, preferably by from one to three substituents per molecule.

The cycloolefins can also be polymerized in the presence of acyclic monoolefins or diolefins, alkines and carbon monoxide. Suitable acyclic olefins include C₂ -C₄₀ -α-olefins and C₄ -C₂₄ -diolefins, for example ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and mixtures of these α-olefins and also 1,4-butadiene, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene, 1,19-eicodiene and mixtures of these diolefins. Also suitable are mixtures of a-olefins and diolefins.

Such olefins and diolefins can also be substituted, for example by phenyl, substituted phenyl, halogen, the esterified carboxyl group, the acid anhydride group; compounds of this type are, for example, chloroprene, styrene, methylstyrene, chlorostyrene, fluorostyrene, indene, 4-vinyl-biphenyl, vinylfluorene, vinylanthracene, methyl methacrylate, ethyl acrylate, vinylsilane, trimethylallylsilane, vinyl chloride, vinylidene chloride, tetrafluoroethylene, isobutylene, vinylcarbazol, vinylpyrrolidone, acrylonitrile, vinyl ethers and vinyl esters. Also possible according to the invention are ring-opening polyadditions, for instance of lactones such as ε-caprolactone or δ-valerolactone, or of lactams such as ε-caprolactam. Preferred monomers are: ethylene, propylene, butene, hexene, octene, 1,5-hexadiene, 1,6-octadiene, methyl methacrylate, ε-caprolactone, δ-valerolactone and acetylene.

The catalysts and any cocatalysts can be used either as such in homogeneous form or individually or together in heterogeneous form on supports. The support material can here be of an inorganic or organic nature, for example silica gel, Al₂ O₃, MgCl₂, cellulose derivatives, starch and polymers.

The polymerization can be carried out in solution, in a slurry, in the gas phase or in bulk. It can be carried out either continuously or batchwise. The catalyst can be initially charged and the monomers can be metered in. However, it is also possible for the monomers to be initially charged and the catalyst to be metered in. It is likewise possible for catalyst and monomers to be initially charged or catalyst and monomers to be introduced into the reaction zone in two separate streams.

The polymerization with the aid of the catalysts to be used according to the invention is preferably carried out with exclusion of water and oxygen. Organic solvents suitable for the polymerization in solution include aromatics such as toluene, chlorobenzene, nitrobenzene, chlorinated aliphatic hydrocarbons such as dichloromethane and mixtures thereof.

In the case of a batch process, the catalysts to be used according to the invention can be used in amounts corresponding to a molar ratio of from 10⁻² to 10⁻⁸, based on monomers to be polymerized. If cocatalysts are also to be used, the molar ratio of catalyst/cocatalyst is generally from 1 to 10-6, preferably from 10⁻¹ to 10⁻⁴ (in the case of aluminium-containing cocatalysts) or from 1 to 10⁻¹ (in the case of boron-containing cocatalysts).

The polymerizations can be carried out at temperatures of from -20 to 200° C., preferably from +20 to 160° C.

The polymers can be precipitated by means of non-solvents such as methanol and then dried.

EXAMPLES Examples 1 to 3

Conditions

Cycloolefin: norbomene

Amount: 100 mmol

Solvent: chlorobenzene

Amount: 100 ml

Cocatalyst: hydrolysed trimethylaluminium (MAO)

Amount: 1 mmol

Temperature: 80° C.

Polymerization time: 1 hour

The results are shown in Table 1 below:

                                      TABLE 1                                      __________________________________________________________________________                            Limi-                                                                              Softening point                                                                        Decomposi-                                                    Acti-                                                                               ting vis-                                                                          (° C.) by thermo-                                                               tion tempera-                               Exam-                                                                              Catalyst  Yield                                                                              vity cosity*                                                                            mechanical                                                                             ture (° C.) by                       ple (mmol)    (g/%)                                                                              (t/mol*h)                                                                           η(dl/g)                                                                        analysis TMA                                                                           DSC                                         __________________________________________________________________________     1   NiPh(Ph.sub.2 PCHCPhO)-                                                                  8.6/91.5                                                                           8.6  1.57                                                                               313     463                                             (iPr.sub.3 PCHPh)                                                              0.001                                                                      2   NiPh(Ph.sub.2 PCHCMeO)-                                                                  8.9/94.7                                                                           8.9  1.60                                                                               377     460                                             (iPr.sub.3 PCHPh)                                                              0.001                                                                      3   NiPh(Ph.sub.2 PCHCMeO)-                                                                  5.8/61.7                                                                           5.8  1.40                                                                               280     451                                             (Ph.sub.3 PCH.sub.2)                                                           0.001                                                                      __________________________________________________________________________      *measured in trichloroethylene at 25° C.                          

Examples 4 to 7

Using a method similar to Examples 1 to 3, norbornene was polymerized using the catalyst according to the invention from Example 1 while varying the temperature and monomer/catalyst ratio (Example 5). In all cases, high catalyst activities of up to 18.6 t/mol.h were achieved. The temperature enables the achievable molar masses/limiting viscosities to be controlled.

The results are shown in Table 2.

                                      TABLE 2                                      __________________________________________________________________________                                          Polymerization   Limiting                      Catalyst  Cocatalyst                                                                          Monomer                                                                              Solvent                                                                            Temperature                                                                           time   Yield                                                                               Activity                                                                            viscosity                                                                           TMA,                Example                                                                             (mmol)    (mmol)                                                                              (mmol/bar)                                                                           (ml)                                                                               (° C.)                                                                         (h)    (g/%)                                                                               (t/mol)                                                                             (dl/g)                                                                              DSC                 __________________________________________________________________________     4    NiPh(Ph.sub.2 PCHCPhO)-                                                                  MAO  Norbornene                                                                           Chloro-                                                                            0° C. bath,                                                                    1       4.9/52.1                                                                           4.9  2.68 295°                                                                    C.                       (iPr.sub.3 PCHPh)                                                                        1    100   benzene                                                                            exothermic to                450°                                                                    C.                                            100 5° C.                                     5    NiPh(Ph.sub.2 PCHCPhO)-                                                                  MAO  Norbornene                                                                           Chloro-                                                                            20     1      18.6/28.3                                                                           18.6 2.63 405°                                                                    C.                       (iPr.sub.3 PCHPh)                                                                        7    700   benzene                          464°                                                                    C.                       0.001                700                                                  6    NiPh(Ph.sub.2 PCHCPhO)-                                                                  MAO  Norbornene                                                                           Chloro-                                                                            40° C., briefly                                                                1       8.5/90.4                                                                           8.5  2.36 289°                                                                    C.                       (iPr.sub.3 PCHPh)                                                                        1    100   benzene                                                                            exothermic to                455°                                                                    C.                       0.001                100 60° C.                                    7    NiPh(Ph.sub.2 PCHCPhO)-                                                                  MAO  Norbornene                                                                           Chloro-                                                                            60° C., briefly                                                                1       8.6/91.5                                                                           8.6  1.89 408°                                                                    C.                       (iPr.sub.3 PCHPh)                                                                        1    100   benzene                                                                            exothermic to                463°                                                                    C.                       0.001                100 74° C.                                    __________________________________________________________________________      All polymers obtained from Examples 1 to 7 are soluble in chlorobenzene.  

I claim:
 1. A method for the polymerization of cycloolefins, which comprises polymerizing said cycloolefins in the presence of a catalyst which is a reaction product ofA. a nickel(0) compound or a compound which can be converted in situ into a nickel(0) compound, with, optionally, B. a compound of the formula ##STR6## and (obligatorily) C. a compound of the formula ##STR7## where R¹ to R⁶ are, independently of one another, straight-chain or branched C₁ -C₂₀ -alkyl, C₁ -C₂₀ -alkoxy, C₃ -C₈ -cycloalkyl, C₂ -C₂₀ -alkenyl, di-(C₁ -C₄ -alkyl)amino, C₆ -C₁₂ -aryloxy, C₇ -C₁₅ -aralkyl, C₇ -C₁₅ -aralkoxy or C₆ -C₁₂ -aryl,E and Q are, independently of one another, nitrogen, phosphorus, arsenic or antimony, X is oxygen, sulphur, ═NR⁹, ═CR⁹ R¹⁰, ═C═C═O, ═C═C═S, ═C═PR¹ R² R³, Y is oxygen or NR⁹, R⁷, R⁸ are, independently of one another, hydrogen, C₁ -C₂₀ -alkyl, C₂ -C₂₀ -alkenyl, C₁ -C₂₀ -alkoxy, C₃ -C₈ -cycloalkyl, C₆ -C₁₂ -aryl, C₆ -C₁₂ -aryloxy, C₆ -C₁₂ -ar-C₁ -C₂₀ -alkyl, C₆ -C₁₂ -ar-C₁ -C₂₀ -alkoxy, C₁ -C₂₀ -alkyl-C₆ -C₁₂ -aryl, C₁ -C₂₀ -alkyl-C₆ -C₁₂ -aryloxy, chlorine, cyano, NHR¹², NR¹² ₂, OR¹², COOR¹², COOR¹¹, CONR¹², COR¹², SR¹², SO₂ R¹², OSO₂ R¹², P(O)(OR¹²)_(2-y) R¹³ _(y), R⁷ may also be SO₃ R¹¹ or R⁷ and R⁸ together with the two carbon atoms to which they are bound form an isocyclic or heterocyclic ring, R⁹ and R¹⁰ are, independently of one another, R¹ or hydrogen, silyl, acyl, chlorophenyl, nitrophenyl, C₁ -C₆ -alkylphenyl, cyano, phenyl-C₂ -C₆ -alkenyl, silyl, trihalogenosilyl, tri-C₁ -C₃₀ -organosilyl, C₁ -C₁₆ -acyl, cyano, halogen, tri-C₁ -C₃₀ -organostannyl, -BH₂, di-C₁ -C₂₀ -organoboranyl, dihalogenoboranyl, R¹¹ is an alkali metal, thallium, 1/2 alkaline earth metal, ammonium, phosphonium, C₁ -C₁₂ -alkyl or C₆ -C₁₂ -aryl, R¹², R¹³ are, independently of one another, C₁ -C₂₀ -alkyl, C₂ -C₂₀ -alkenyl, C₃ -C₈ -cycloalkyl or C₆ -C₁₂ -aryl and y is zero, 1 or
 2. 2. Method according to claim 1, wherein the reaction product has the structural feature ##STR8##
 3. Method according to claim 1, wherein the reaction product has the formula whereE, Q, X, Y and R¹ to R⁸ are as defined in claim
 1. 4. Method according to claim 1 in the presence of an acid cocatalyst.
 5. Method according to claim 1 at a temperature of from -20 to 200° C. 